Styrenated oil, styrene oxidephenol resin, drying oil coating composition



Patented May 27, 1952 STYRENATED OIL, STYRENE OXIDE- PHENOL RESIN, DRYING \OIL COATING COMPOSITION Paul E. Marling, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application September 29, 1948, Serial No. 51,859

3 Claims.

This invention relates to new improved coating compositions readily prepared from inexpensive and abundantly available raw materials. More particularly the invention relates to selfdrying film forming compositions involving styrenated oils and resins prepared bythe condensation of styrene oxide with phenols.

The paint and varnish industry has been seeking to adapt styrene to coating composition use because of its low cost and availability. Many of the developed coating compositions are too brittle for general utility, and others are only suitable for preparation of pigmented films because of the opacity resulting from the incompatibility of the styrenated oils with many commonly used resins and other coating composition components. It is also known that transparent drying oil substitutes can be prepared from styrene by interpolymerizing it with drying oils by specialized procedures. Compounds of this type are commercially available and are known to the industry as styrenated oils. Although for many purposes the available styrenated oils are suitable, there are numerous formulations, particularly with phenolic resins in varnishes, where the incompatibility restricts their general utility.

The primary purpose of this invention is to provide new transparent coating compositions from styrene and related monomers. A further purpose is to provide a coating composition of unusual resistance to thermo softening and to the action of organic solvents, water, and alkali.

The expression styrenated oils, as used in the protective coating industry and in this specification, means a copolymer of a natural drying oil and a styrene type of monomer, such as styrene, a-methylstyrene, vinylbiphenyl and isopropenylbiphenyl. Suitable natural oils are the drying oils or the semi-drying oils, including linseed oil, soy oil, tung oil and dehydrated castor oil. The copolymers are prepared by polymerization at elevated temperatures, preferably in the presence of peroxide catalysts, such as benzoyl peroxide, acetyl peroxide, t-butylhydroperoxide, isopropyl percarbonate and homologues thereof soluble in the mixed monomers or in the polymerization medium. The catalysts may be present to the extent of from 0.01 to five percent by weight, based on the combined monomers, but the preferred proportion of catalyst will depend upon the extent of polymerization required to bring the copolymer up to the desired viscosity at a pre-determined temperature. The proportion of the monomers and the original viscosity of the drying oil being used will also influence the quantity of catalyst required to attain the deired viscosity. Generally from 25 to 75 percent by weight, of vinyl or isopropenyl aromatic derivative, and 75 to 25 percent dryingoil will roduce a beneficial result. Optimum properties will be secured by using the preferred proportion of to 60 percent of either component.

The styrenated oils may be prepared by refluxing the drying oil with an inert solvent or diluent, such as xylene, benzene, toluene, dioxane, or petroleum ether, in the presence of an organic peroxide, and adding the vinyl (or isopropenyl) aromatic hydrocarbon gradually until a predetermined viscosity is achieved, the end-point viscosity being that which will yield a desired viscous liquid copolymer after evaporation of the inert solvent or diluent.

An alternative method of preparing the styrenated oil involves heating a mixture of the drying oil and the vinyl or isopropenyl aromatic hydrocarbon and heating them until the monomer is copolymerized to the desired extent as determined by the measured viscosity. Where an active monomer, such as styrene, is used, from 5 to 40 percent of a less active monomer, such as an isopropenyl derivative should be included to retard polymerization.

In United States Patent 2,422,637, issued June 17, 1947, to Charles A. Thomas, there is described and claimed a resinous composition suitable for the preparation of varnishes by dissolution in drying oils. The resinous composition is made by condensing styrene oxide with phenol or a -alkyl phenol, such as p-cresol, p-ethyl phenol, p-t butylphenol, p-isopropylphenol or other p-alkyl phenol having up to six carbon atoms in the alkyl radical.

The styrene oxide-phenol condensation resin is prepared by heating the phenolic constituent and gradually adding a readily desired quantity of styrene oxide, for example from 50 to 200 percent by weight of the phenol, from one to four hours being required for the addition. The temperature required will be froml20 C. to about 225 C., precautions being taken to keep the reaction rate under control, a rapid but not vigorous reaction has been found to produce the best result. After the completion of the reaction further heating at reduced pressures will assist in the removal of unreacted monomers and water produced by the polymerization reaction.

It has been found that coating compositions useful in the preparation of clear, transparent surface films of unusual quality, may be prepared t by dissolvingin styrenated oils the resins prepared by condensing the aralkylene oxide phenolic resins. Useful coating compositions are preparedf by utilizing one to ten parts by weight ofv either component, but, WhiQh may in addition include 3 from one totten' partsjnormal orbodied natural drying oil's/such as linseed oil, soy oil, oiticia oil,

dehydrated castor oil and chinawood oil.

The new varnishes maybe dried in air, but ac- V celerated drying may be induced by. heating in a 7 suitable air circulation oven, or in the'o'pen under infra red lamps. Accelerated room temperature drying may be achieved by the incor- The above tabulation of data indicates that styrenated oil cannot be compounded with phenolformaldehyde resins in the manner conventional in the varnish industry. By'using the" Y r nsparency.

porationpof conventional driers, for; example the;

1 lead, cobalt, and manganese naphthenates, or 1 similar heavy metal salts- If colored coatings are requiredconventional dyes and pigments may be added; The coating'compositions mayv also be thinned by the incorporation of conven R tional 'diluents, such as turpentine, mineral s ir s. tan aa hthe an Xylene, the uanrequired. for

methqdq errl ceiiq pt m la d- 1 F rth a ls. o h

th shes twe t gown with respect to the followm 0 he egample 7 An Qilsoluble;phenolformaldehyde resin was;

ed d

direz tdily by the determines preparation and use of p the particularg prep d s lvlediin tung'oil in the proportion dpounds for each gallons 7 us soliit'on repared was then mixed with an equal w ht o a friigzture of 80 percent min-f P I? FiF ren Xy e A si i varnish was prepared in anidenticaljmanner 'ex-f 7 ha 2' e oxiqgnhen condensation: in pla cego f theprphenolformalde-g aghotthe two resin solutions were:

blex fle i n reru s-em orium. w a 'Styrenated g f mfihe aflws en e aq rfifqe ithinl r n -1- i... w tyou ur The following table indica es the; properties of 41? PP19451P1$Q2QPQR 1 7 i T, .Bhendi i v ene q V V tyrenatedOils' .dehydeResln Phenol Resin F 0.03%Cobalt' inTung'OiI 'in Tung Oil Film Prop Pe n y. z ie e zbyq ;e c flt v cities Weight p NYeight of vWeight of j r Res'in -Resin i V V V 0- 0 Clear.

10 0 Opaque 21 0 Do. 35 0 Do. a '3- '2 r o. 67 V 0' 'Do.

100.1 0 Clear. 1

*0 10 Do. 0.2 21 'Do. V 35 Do. 0 r 45 Do. 01 Y 50 Do; .0 7 Do. 7-

H W tingi'thedisso1uti0n the mixture, w heated at SOO FUfortWenty minutes. The

dr n Q11 q ntai n 0-03 Pe t b 1 a ='-T t tcfa lita e n A11 ,1

V of a compound, selecte 7 Number c aims,

Iclaim: V r V I h Y1. A coating composition comprising (A) a soluble copolymer of from 25 to percent by weight of; styrene and from 75 to 25 percent of a natural drying oil, (B) 'a;natural drying oil and (C) a condensation product of phenol andfrom 0 2 P r ent ase n the ph c o sty ene Oxide 2." 'A coating. omp siti nc mprising. (4),..Qne f.

of phenol weir-9 the phenol, ofstyreneo r A m ibqsitwh. com r n u e c w m Q75 R FQWQQ we d; from; he Q??? 1 9 2 r a v ny bip f m l-iin i 21-. (a a Q11. n (C) ar s i rep e b z-conden n tyrene wherein R is'a ra hydrogen and a1; bonatoms. V f r 1 qnz g The following. referencesare of record inthe file of. this patentq V TED silt-Art a ns;

V gate 32 3 H 21 9!, 2,382,213 Aug. 14, 1 9 45 2,392,710 2,422,637 7 1.7, 11m:

7 4 7 48 l u Tr,

opting REFERENCES l h invention is defined by the following 

3. A COATING COMPOSITION COMPRISING (A) A SOLUBLE COPOLYMER OF 25 TO 75 PERCENT BY WEIGHT OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF STYRENE, A-METHYLSTYRENE, VINYLBIPHENYL AND ISOPROPENYLBIPHENYL; AND 75 TO 25 PERCENT OF A NATURAL DRYING OIL, (B) A NATURAL DRYING OIL, AND (C) A RESIN PREPARED BY CONDENSING STYRENE OXIDE AND A PHENOL OF THE FORMULA: 